Silylating grafting agents, polymers grafted therewith and methods of synthesis

Abstract

Silylating grafting agents and methods for synthesizing the same. The grafting agents are used to produce functionalized polydiene polymers by modifying the backbone of the polymer. Methods for functionalizing a polydiene post-polymerization using hydrosilylation are described. Hydrosilylation provides an advantage of incorporating multiple functional groups on the backbone of the polymer which lead to improved properties, such as rolling resistance, wet traction and polymer filler interaction.

What is claimed is: 
     
         1 . A method for synthesizing a silylating grafting agent, comprising the steps of:
 combining a siloxane, a compound having a vinyl group with substitution at one carbon atom of the double bond, and a catalyst suitable for facilitating reaction between the siloxane and the compound; and   reacting the siloxane and the polar compound for a sufficient period of time to produce the grafting agent;   wherein the siloxane has the following formula:   
       
         
           
           
               
               
           
         
       
       wherein n is an integer from 0 to 8, and each R individually is a hydrogen atom, a halogen atom, or a monovalent organic group, or where two or more R groups join to form a bond or a polyvalent organic group, with the proviso that each compound contains at least two R groups which are hydrogen atoms, bonded to different silicon atoms, or 
       
         
           
           
               
               
           
         
         wherein R is a hydrogen atom, a halogen atom and n is 2 to 5. 
       
     
     
         2 . The method according to  claim 1 , wherein the compound is a polar compound having the formula CH 2 =CHCH 2 X—R, wherein X is O or N, and wherein R is polyethylene oxide having from 3 to 100 repeat groups, or is derived from piperidine when X is N or is derived from bis(trimethylsilyl)amine when X is N,
 wherein the catalyst is one or more of an organo metal compound, salt or metal, and 
 wherein the metal comprises Ni, Ir, Rh, Ru, Os, Pd and Pt compounds. 
 
     
     
         3 . The method according to  claim 2 , wherein the polar compound is one or more of i.) allyloxy(polyethylene oxide) methyl ether wherein the polyethylene oxide has from 1 to 100 repeat units; ii.) 1-allylpiperidine; and iii.) N-allyl-N,N-bis(trimethylsilyl)amine, and
 wherein the catalyst is one or more of chloro(1,5-cyclooctadiene)rhodium(I), platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane.   
     
     
         4 - 5 . (canceled) 
     
     
         6 . The method according to  claim 1 , wherein the reaction is performed at a temperature between about −5° C. and about 100° C.,
 wherein the siloxane, compound and catalyst are combined in a reaction vessel, and 
 wherein the reaction vessel is vented to remove H2 gas, and further including the step of removing the catalyst after the reaction step. 
 
     
     
         7 - 8 . (canceled) 
     
     
         9 . The method according to  claim 1 , wherein the reaction is performed in solvent that is hexane or toluene. 
     
     
         10 . A grafting agent produced by the method according to  claim 1 . 
     
     
         11 . A method for functionalizing a polydiene post-polymerization using hydrosilylation, comprising the steps of:
 reacting i) the polydiene with ii) a silylating grafting agent having the formula:   
       
         
           
           
               
               
           
         
       
       wherein n is an integer from 0 to 8, 25 or 150, and each R individually is a hydrogen atom, a halogen atom, a monovalent organic group, or an Fg (as defined below) or where two or more R groups join to form a bond or a polyvalent organic group, with the proviso that at least one R is a hydrogen atom;
 wherein Fg is derived from a compound having the formula CH 2 =C(R 1 )(R 2 ), wherein at least one of R 1  and R 2  have a functionality that may participate in hydrogen bonding, a chemical reaction with a filler or polymer grafting and one of R 1 , and R 2  may be a hydrogen atom or an organic group, or 
 
       
         
           
           
               
               
           
         
         wherein R is a hydrogen atom, a halogen atom, a monovalent organic group, or another Fg, and wherein Fg is as defined above, and n is 2 to 5. 
       
     
     
         12 . The method according to  claim 11 , wherein the compound has the formula CH 2 =CHCH 2 X—R, wherein X is O or N, and wherein R is polyethylene oxide having from 3 to 100 repeat groups, or is derived from piperidine when X is N or is derived from bis(trimethylsilyl)amine when X is N. 
     
     
         13 . The method according to  claim 11 , wherein the polydiene comprises one or more of poly(1,3-butadiene) and a copolymer of butadiene and a comonomer that is one or more of an aromatic vinyl compound and a conjugated diene, wherein the aromatic vinyl compound is styrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2,4-dimethylstyrene, 2,4,6-trimethylstyrene, alpha-methylstyrene, 2,4-diisopropylstyrene, 4-tert-butylstyrene, stilbene, vinyl benzyl dimethylamine, (4-vinylbenzyl)dimethyl aminoethyl ether, N,N-dimethylaminoethyl styrene, tert-butoxystyrene, vinylpyridine, 1,2-divinylbenzene, 1,3-divinylbenzene or 1,4-divinylbenzene, or a combination thereof, wherein the aromatic vinyl compound constitutes from 0 to 50 wt. % of the total monomer content of the copolymer. 
     
     
         14 . The method according to  claim 13 , wherein the conjugated diene is isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2,4-hexadiene, 1,3-hexadiene, 1,3-heptadiene, 1,3-octadiene, 2-methyl-2,4-pentadiene, cyclopentadiene, 2,4-hexadiene, 1,3-cyclohexadiene or 1,3-cyclooctadiene, or a combination thereof, and
 wherein the copolymer is styrene-butadiene rubber, butadiene-isoprene rubber or butadiene-isoprene-styrene rubber, wherein when styrene is present the styrene content is of from 5 wt. % to 50 wt. % by weight of total monomer content of the copolymer.   
     
     
         15 . (canceled) 
     
     
         16 . The method according to  claim 11 , further including the step of terminating a living chain end of the polymer with a terminator and/or coupling two or more living chains together with a coupling agent and/or quenching a living chain end of the polymer with a quenching agent prior to reacting the i) polydiene with ii) the silylating grafting agent. 
     
     
         17 . The method according to  claim 16  wherein the terminator is one or more of carbon dioxide, a benzophenone, a benzaldehyde, an imidazolidone, a pyrrolidinone, a carbodiimide, an urea, a isocyanate, a Schiff base, a trialkyltin halide, a cyclic amino compound, a N-substituted aminoketone, a N-substituted thioaminoketone, a N-substituted aminoaldehyde, a N-substituted thioaminoaldehyde, a sulfur-containing or oxygen containing azaheterocycle, a boron-containing terminator, a cyclic siloxane, a α-halo-ω-amino alkane, a trialkylsilyl halide, an arylsilyl halide and a alkyl-aryl silyl halide, and wherein the coupling agent is one or more of the following: R* n M 1 Y (4-n) , M 1 Y 4 , and M 2 Y 3  wherein each R* is independently a monovalent organic group having 1-20 carbon atoms; M 1  is a tin atom, silicon atom or germanium atom; M 2  is a phosphorous atom; Y is a halogen atom, an alkoxysilane and/or carboxysilane; and n is an integer of 0-3. 
     
     
         18 . The method according to  claim 11 , wherein the catalyst is one or more of an organo metal compound, salt or metal, and wherein the metal comprises Ni, Ir, Rh, Ru, Os, Pd and Pt compounds,
 wherein the average number of grafted units per chain is from about 0.25 to about 15, and   wherein grafting of nitrogen containing functional groups onto main chain varies from 50 ppm to 2200 ppm per polymer chain.   
     
     
         19 . The method according to  claim 11 , wherein the catalyst is platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane, and wherein the reaction is performed in a solvent that is a hydrocarbon solvent. 
     
     
         20 - 22 . (canceled) 
     
     
         23 . A hydrosilyl-functionalized polydiene polymer, comprising:
 a reaction product of i) a polydiene and ii) a silylating grafting agent having the formula:   
       
         
           
           
               
               
           
         
       
       wherein n is an integer from 0 to 8, 25 or 150 and each R individually is a hydrogen atom, a halogen atom, a monovalent organic group, or an Fg (as defined below) or where two or more R groups join to form a bond or a polyvalent organic group, with the proviso that at least one R is a hydrogen atom;
 wherein Fg is derived from a compound having the formula CH 2 =C(R 1 )(R 2 ), wherein at least one of R 1  and R 2  have a functionality that may participate in hydrogen bonding, a chemical reaction with a filler or polymer grafting and one of R 1 , and R 2  may be a hydrogen atom or an organic group, or 
 
       
         
           
           
               
               
           
         
         wherein R is a hydrogen atom, a halogen atom, or a monovalent organic group, or another Fg, and wherein Fg is as defined above, and n is 2 to 5 
       
     
     
         24 . The polymer according to  claim 23 , wherein the compound has the formula CH 2 =CHCH 2 X—R, wherein X is O or N, and wherein R is polyethylene oxide having from 3 to 100 repeat groups, or is derived from piperidine when X is N or is derived from bis(trimethylsilyl)amine when X is N. 
     
     
         25 . The polymer according to  claim 23 , wherein the polydiene comprises one or more of poly(1,3-butadiene) and a copolymer of butadiene and a comonomer that is one or more of an aromatic vinyl compound and a conjugated diene, wherein the aromatic vinyl compound is styrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2,4-dimethylstyrene, 2,4,6-trimethylstyrene, alpha-methylstyrene, 2,4-diisopropylstyrene, 4-tert-butylstyrene, stilbene, vinyl benzyl dimethylamine, (4-vinylbenzyl)dimethyl aminoethyl ether, N,N-dimethylaminoethyl styrene, tert-butoxystyrene, vinylpyridine, 1,2-divinylbenzene, 1,3-divinylbenzene or 1,4-divinylbenzene, or a combination thereof, wherein the aromatic vinyl compound constitutes from 0 to 50 wt. % of the total monomer content of the copolymer. 
     
     
         26 . The polymer according to any of  claim 25 , wherein the conjugated diene is 1,3-butadiene, 2-(C1-C5 alkyl)-1,3-butadienes such as isoprene (2-methyl-1,3-butadiene), 1,3-pentadiene, 2,4-hexadiene, 1,3-hexadiene, 1,3-heptadiene, 1,3-octadiene, 2-methyl-2,4-pentadiene, cyclopentadiene, 2,4-hexadiene, 1,3-cyclohexadiene or 1,3-cyclooctadiene, or a combination thereof, and
 wherein the copolymer is styrene-butadiene rubber, butadiene-isoprene rubber or butadiene-isoprene-styrene rubber, with a styrene content of from 5 to 50% by weight of total monomer content of the copolymer.   
     
     
         27 . (canceled) 
     
     
         28 . The polymer according to  claim 23 , the average number of grafted units per chain is from about 0.25 to about 15, alternatively from about 2 to about 8. 
     
     
         29 . The polymer according to  claim 23 , wherein grafting of nitrogen containing functional groups onto main chain varies from 50 ppm to 2200 ppm per polymer chain, or
 wherein the polymer has a weight average molecular weight of about 75,000 q/mol to about 1,000,000 g/mol, or   wherein the polymer has a number average molecular weight of about 75,000 q/mol to about 1,000,000 g/mol.   
     
     
         30 - 31 . (canceled)